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Here, we report a rational design of D\u2013A\u2013type additives (UV326\u2010DBOPA and UV327\u2010DBOPA) that modulate morphology and transfer ultraviolet (UV) photons into utilizable photoexcitations through an energy\u2010transfer process in the active layer, thereby simultaneously enhancing device performance and suppressing photodegradation. In PM6: Y6 and PM6: L8\u2010BO systems, the power conversion efficiencies (PCE) reach 16.1% and 17.5%, respectively, accompanied by markedly prolonged lifetimes under continuous UV illumination. Further analysis reveals that the structure of D\u2013A\u2010type additives substantially influences molecular packing and the associated energy\u2010transfer pathways. The less self\u2010aggregated UV326\u2010DBOPA provides a superior efficiency and stability by enabling optimized intermolecular packing and intrinsic energy transfer within the photoactive layer. 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